CN110894300A - Polyacid hybrid material based on rigid nitrogen-containing ligand, preparation method and application - Google Patents

Polyacid hybrid material based on rigid nitrogen-containing ligand, preparation method and application Download PDF

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CN110894300A
CN110894300A CN201911269972.XA CN201911269972A CN110894300A CN 110894300 A CN110894300 A CN 110894300A CN 201911269972 A CN201911269972 A CN 201911269972A CN 110894300 A CN110894300 A CN 110894300A
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谢景力
徐昊
潘伟
张俊勇
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Jiaxing University
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Abstract

The invention discloses a preparation method of a polyacid hybrid material based on a rigid nitrogen-containing ligand, which is a hybrid material obtained by performing hydrothermal treatment on a mixture consisting of heteropoly acid, copper salt, the rigid nitrogen-containing ligand and water after regulating and controlling the pH value, wherein the rigid nitrogen-containing ligand is 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole). The invention discloses a polyacid hybrid material based on a rigid nitrogen-containing ligand and application thereof as a photodegradation catalyst for degrading rhodamine B. The method has the beneficial effect of degrading rhodamine B through photocatalysis.

Description

Polyacid hybrid material based on rigid nitrogen-containing ligand, preparation method and application
Technical Field
The invention relates to the technical field of polyacid hybrid material preparation. More specifically, the invention relates to a polyacid hybrid material based on a rigid nitrogen-containing ligand, a preparation method and an application thereof.
Background
With the rapid development of modern printing and dyeing industry, the types and the amount of compounds entering water through various ways are increased rapidly, and organic wastewater contains a plurality of pollutants which are difficult to degrade and have toxicity, wherein rhodamine B has the characteristics of high degradability, easy accumulation and the like, and poses serious threats to ecosystem and human health. In order to realize the effective degradation of rhodamine B in organic wastewater, the design of a photodegradation catalyst is a core problem.
Polyoxometalates (POMs, also known as polyacids) are inorganic compounds that have wide applications in the fields of catalysts, biology, medicine and material science, have various special electrical and optical properties, such as electrochromic, photochromic, reversible redox activity, etc., and become important inorganic building elements for constructing novel functional crystalline materials.
The metal-organic coordination polymer is a framework compound which is formed by self-assembling metal central ions and organic ligands and has a periodic network structure, wherein the framework compound comprises a one-dimensional (1-D), two-dimensional (2-D) or three-dimensional (3-D) structure. It is different from simple complexes and general inorganic compounds or organic polymer compounds, and it can contain various metal ions and organic ligands, thus having variety and special physical and chemical properties. Its development relies on the design and synthesis of metal-organic coordination polymers with novel structures and properties. The diversity of the composition and structure of a substance determines its diversity of properties. The complexity of the structure may make it uniquely functional. In order to explain the nature and structure of the complex, people go through the process of becoming deeper from superficial to deep, and learning, practicing, learning again and practicing again. Through the experimental facts collected, an appropriate theory is used to explain and link all the facts, however, the theory is changed or corrected as more materials are obtained, and even a new theory is completely abandoned and created. We can get enlightening from the exploration thinking evolution of the former people, get innovative inspiration, learn the shortage (deficiency) of thinking mode in filling and developing theory, learn to break through old constraint, open up new places, and promote the creation and development of new theory. This is the teaching we should gain in learning the theoretical development of the complex. Therefore, how to design and synthesize the polyoxometallate compound which has a novel structure and has the catalytic performance of photodegradation is one of the hot spots of researches of crystal engineers and coordination chemists at present.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.
The invention also aims to provide a preparation method of the polyacid hybrid material based on the rigid nitrogen-containing ligand, which takes the rigid nitrogen-containing ligand 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) as the ligand, has simple preparation method and high yield, and batch samples of the two compounds are single pure phase.
It is also an object of the present invention to provide a polyacid hybrid material based on a rigid nitrogen-containing ligand, comprising compound 1 (formula C)10Cu2N6O23Si0.5W6Na0.25) And compound 2 (chemical formula is C)5H4Cu1.25N3O), both of which have the effect of degrading rhodamine B by photocatalysis.
The invention also aims to provide application of the polyacid hybrid material based on the rigid nitrogen-containing ligand as a photodegradation catalyst for degrading rhodamine B.
To achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, there is provided a method for preparing a polyacid hybrid material based on a rigid nitrogen-containing ligand, the hybrid material being obtained by subjecting a mixture of a heteropoly acid, a copper salt, a rigid nitrogen-containing ligand and water to a hydrothermal treatment after adjusting the pH, wherein the rigid nitrogen-containing ligand is 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole).
Preferably, the heteropolyacid is SiW12The copper salt is Cu (NO)3)2·3H2The preparation method specifically comprises the following steps:
adding Cu (NO)3)2·3H2O，SiW12Adding 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) and water into a high-pressure stainless steel reaction kettle with a polytetrafluoroethylene lining, adjusting the pH value to 3.5, sealing and thenPlacing the reaction kettle in an oven, reacting at 160 ℃ for 3 days, and purifying to obtain the Cu (NO)3)2·3H2O、SiW12The mol volume ratio of the 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) to the water is 0.5 mmol: 0.1 mmol: 0.1 mmol: 10 mL.
Preferably, HNO is used3The solution and NaOH solution were used to adjust the pH.
Preferably, the heteropolyacid is PMo12The copper salt is Cu (OAc)2The preparation method specifically comprises the following steps:
general formula (Cu), (OAc)2，PMo12Adding 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) and water into a polytetrafluoroethylene-lined high-pressure stainless steel reaction kettle, adjusting the pH to 4.5, sealing, placing the reaction kettle in an oven, reacting at 160 ℃ for 3 days, and purifying to obtain the compound, wherein Cu (OAc)2、PMo12The mol volume ratio of the 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) to the water is 1.2 mmol: 0.075 mmol: 0.2 mmol: 10 mL.
Preferably, the pH is adjusted with HCl and NaOH solutions.
A polyacid hybrid material based on rigid nitrogen-containing ligand, prepared by the preparation method of claim 3, and having chemical formula C10Cu2N6O23Si0.5W6Na0.25Wherein the crystal system is a monoclinic system; space group is P21C; unit cell parameter of
Figure BDA0002313891170000031
α＝90°、β＝105.001(4)°、γ＝90°、Z＝4。
A polyacid hybrid material based on rigid nitrogen-containing ligand, prepared by the preparation method of claim 5, and having chemical formula C5H4Cu1.25N3O, wherein the crystal system is a tetragonal crystal system; space group I41(ii)/amd; unit cell parameter of
Figure BDA0002313891170000032
α＝90°、β＝90°、γ＝90°、Z＝16。
An application of a polyacid hybrid material based on a rigid nitrogen-containing ligand as a photodegradation catalyst for degrading rhodamine B.
The invention at least comprises the following beneficial effects:
the preparation method is simple, the yield is high, and batch samples of the two compounds are single pure phase;
the compound 1 and the compound 2 prepared by using the rigid nitrogenous ligand 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) in combination with heteropoly acid and copper salt have the beneficial effect of strong catalytic degradation capability on rhodamine B.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a graph comparing theoretical and experimental X-ray powder diffraction patterns of Compound 1 of the present invention;
FIG. 2 is a graph comparing theoretical and experimental X-ray powder diffraction patterns of Compound 2 of the present invention;
FIG. 3 is a diagram showing the coordination environment of Cu in the compound 1 according to the present invention;
FIG. 4 is a schematic view of the 1-D chain structure of the compound 1 of the present invention;
FIG. 5 is a 2-D plan structural view of the compound 1 of the present invention;
FIG. 6 is a diagram showing the coordination environment of Cu in the compound 2 according to the present invention;
FIG. 7 is a schematic view of the 2-D layer structure of Compound 2 of the present invention;
FIG. 8 is a 3-D pore structure diagram of Compound 2 of the present invention;
FIG. 9 is a chart of the infrared spectrum of Compound 1 of the present invention;
FIG. 10 is a chart of the infrared spectrum of Compound 2 of the present invention;
FIG. 11 is a photodegradation spectrum of the Compound 1 of the present invention;
fig. 12 is a photodegradation spectrum of the compound 2 of the present invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
< example 1>
The polyacid hybrid material based on rigid nitrogen-containing ligand is a compound 1, and the chemical formula of the compound 1 is C10Cu2N6O23Si0.5W6Na0.25Wherein the crystal system is a monoclinic system; space group is P21C; unit cell parameter of
Figure BDA0002313891170000041
α＝90°、β＝105.001(4)°、γ＝90°、Z＝4。
The preparation method of the compound 1 comprises the following steps: adding Cu (NO)3)2·3H2O(0.5mmol)，SiW12(0.1mmol), 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) (0.1mmol) and 10mL of water were added to a polytetrafluoroethylene-lined high pressure stainless steel reactor, using HNO3Adjusting the pH value of the solution and NaOH solution to 3.5, sealing, placing the reaction kettle in an oven, reacting for 3 days at 160 ℃, washing with clear water, and performing ultrasonic filtration to obtain dark blue blocky crystals with the yield of 81.3%.
< example 2>
The polyacid hybrid material based on the rigid nitrogen-containing ligand is a compound 2, and the chemical formula of the compound 2 is as follows: c5H4Cu1.25N3O, wherein the crystal system is a tetragonal crystal system; space group I41(ii)/amd; unit cell parameter of
Figure BDA0002313891170000042
Figure BDA0002313891170000043
α＝90°、β＝90°、γ＝90°、Z＝16。
The preparation method of the compound 2 comprises the following steps:
general formula (Cu), (OAc)2(1.2mmol)，PMo12(0.075mmol), 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) (0.2mmol) and 10mL of water were added to polytetrafluoroethyleneIn a lined high-pressure stainless steel reaction kettle, adjusting the pH value to 4.5 by using HCl solution and NaOH solution, sealing the reaction kettle, putting the reaction kettle in an oven, reacting for 3 days at 160 ℃, washing by using clear water, and performing ultrasonic filtration to obtain strip-shaped tawny crystals with the yield of 80.6 percent.
Experiment of
1. Powder X-ray diffraction characterization of phase purity
X-ray powder characterization of Compound 1 prepared in example 1 and Compound 2 prepared in example 2, respectively, X-ray powder diffraction (PXRD) data of Compound 1 and Compound 2 were obtained by using a super diffractometer having D/teX and Cu K α
Figure BDA0002313891170000044
The Ultima IV of the radiation source was measured at 30kV and 20 mA.
And (3) comparison finding:
as shown in fig. 1-2, the results of the experimentally determined X-powder diffraction data of the crystals of compound 1 and compound 2 and the corresponding theoretical diffraction data are matched at the main positions, so that it can be demonstrated that the bulk samples of both compounds (compound 1 and compound 2) are single pure phase.
The difference in diffraction peak intensity may be due to changes in the preferred orientation of the powder during data collection in the experimental PXRD pattern.
2. Determination of Crystal Structure
The crystals of the target compound were selected from Compound 1 prepared in example 1 and Compound 2 prepared in example 2 and observed at room temperature by microscope, and X-ray diffraction experiments were conducted at room temperature, respectively
Figure BDA0002313891170000051
Figure BDA0002313891170000052
At a temperature of 296K to
Figure BDA0002313891170000053
The method collects diffraction data, the diffraction data of partial structure is absorbed and corrected by SADABS program, the crystal structure is solved by combining direct method with difference Fourier, all non-hydrogen atom coordinates and anisotropic parameters are corrected by full matrix least square method, the position of C-H atom is calculated and determined according to theoretical mode, O-H atom is firstly found out according to difference Fourier, then the hydrogen atom coordinates and isotropic parameters are corrected by full matrix least square and participate in final structure refinement, concretely, the following table shows that:
TABLE 1 crystallographic data and structural parameters for Compound 1 and Compound 2
Figure BDA0002313891170000054
Figure BDA0002313891170000061
TABLE 2 key length of Compound 1
Figure BDA0002313891170000062
Figure BDA0002313891170000063
Figure BDA0002313891170000071
Figure BDA0002313891170000081
TABLE 3 major bond lengths of Compound 2
Figure BDA0002313891170000082
Figure BDA0002313891170000083
TABLE 4 Main bond Angle (o) of Compound 1
Figure BDA0002313891170000084
Figure BDA0002313891170000091
Figure BDA0002313891170000101
TABLE 5 Key Angle (o) of Compound 2
Figure BDA0002313891170000102
Figure BDA0002313891170000111
Analysis of crystal structure of compound 1:
from the single crystal X-ray diffraction analysis combining table 1 and table 2, it can be seen that compound 1 contains two Cu (1) ions and two Cu (2) ions, and the Cu (1) ions and the Cu (2) ions are linked and coordinated by the same O atom in the crystallization water and coordinated with N atoms at two ends of two 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) ligands, respectively, so that the Cu (1) ions and the Cu (2) ions are tetra-coordinated, respectively, and contain six crystallization water molecules in total, and the crystal is in a tetragonal space crystal system P21/c。
The bond valence calculation shows that all Cu ions are in a + II oxidation state, Si atoms are in a + IV oxidation state, W atoms are in a + VI oxidation state, and the bond lengths of Cu-O bonds and Cu-N bonds are in the range of
Figure BDA0002313891170000112
And
Figure BDA0002313891170000113
the adjacent Cu (1) ions and Cu (2) ions are connected with O atoms in the crystal water in a staggered manner and are respectively subjected to four-coordination with the ligand to form a one-dimensional chain structure, and on the basis, the compound 1 continuously extends to the horizontal plane through Cu-O and the ligand 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) to grow into a two-dimensional plane structure as shown in the following figures, particularly as shown in figures 3-5.
Analysis of crystal structure of compound 2:
the single crystal X-ray diffraction analysis shows that the compound 2 contains 4 Cu (2) ions and one Cu (1) ion, 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) ligands and is crystallized in a monoclinic system I41/amd。
The bond valence calculation indicates that all Cu ions are in the + II oxidation state. In the compound 2, Cu (1) ions are respectively in four coordination with four O atoms in the crystal water, and Cu (2) ions are respectively in four coordination with one nitrogen atom on two 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) ligands and two O atoms coordinated with the Cu (1) ions, so that a structure shown in the figure is formed.
The adjacent Cu (2) ions are four-coordinated with the ligand and the O atom in the crystal water in the same coordination mode to form a one-dimensional structure. The Cu (1) ions are respectively in four-coordinate linkage with O atoms in four crystal waters, a two-dimensional layered structure is gradually formed in the longitudinal direction, and a three-dimensional porous structure is continuously grown in the longitudinal direction through the linkage of the Cu (1) ions, as shown in FIGS. 6-8.
To make the structural diagrams (fig. 3-8) more clear, the hydrogen atoms in all structures in the figures have been omitted.
3. Infrared spectroscopic analysis
The infrared spectra of compound 1 prepared in example 1 and compound 2 prepared in example 2 are shown in fig. 9-10, respectively. For infrared measurements, KBr was mixed with the compound at a ratio of 100:1 and the mixture was tableted and measured by a Varian 640 model FT-IR spectrometer. The spectrogram can analyze that:
in compound 1:
3420cm-1the characteristic peak is O-H stretching vibration in hydroxyl;
3130cm-1the characteristic peak is O-H stretching vibration in carboxylic acid
1640cm-1The peak at (A) is 4' - (1, 4-phenyl) bis (4H-1,a characteristic absorption peak of the v as (C-N) in the 2, 4-triazole) ligand;
1150cm-1、1260cm-1is a stretching vibration characteristic absorption peak of the vos (C-H) on a benzene ring;
922～1550cm-1the characteristic peak is C-N, C ═ C stretching vibration.
In compound 2:
3449cm-1the characteristic peak is O-H stretching vibration in hydroxyl;
3110cm-1the characteristic peak is O-H stretching vibration in carboxylic acid
1570cm-1And 1540cm-1The peak at (A) is generally v as (-CH)2) Characteristic absorption peak of (a);
1100cm-1the peak is a stretching vibration characteristic absorption peak of the nuas (C-H) on the benzene ring;
630cm-1，690cm-1and 848cm-1The characteristic peaks can be assigned to characteristic absorption peaks of vos (Mo-Ot), vos (Mo-O-Mo) and vos (P-O).
4. Photodegradability analysis
Fig. 11 is an ultraviolet absorption spectrogram of the compound 1 prepared in example 1 for photocatalytic degradation of rhodamine B, and it is obvious from the chart that the compound 1 has catalytic degradation effect on rhodamine B, that is, in the presence of the compound 1, absorption peaks of rhodamine B solutions are all weakened along with the increase of time, and the longer the illumination time is, the higher the catalytic efficiency is. The degradation rate of the rhodamine B solution after 2.5 hours of illumination reaches 8.26 percent;
fig. 12 is an ultraviolet absorption spectrogram of the compound 2 prepared in example 2 for photocatalytic degradation of rhodamine B, and it is obvious from the figure that the compound 2 has catalytic degradation effect on rhodamine B, that is, in the presence of the compound 2, absorption peaks of rhodamine B solutions are all weakened along with the increase of time, and the longer the illumination time is, the higher the catalytic efficiency is. The degradation rate of the rhodamine B solution after 2.5 hours of illumination reaches 4.41 percent.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (8)

1. The preparation method of the polyacid hybrid material based on the rigid nitrogen-containing ligand is characterized in that the hybrid material is obtained by performing hydrothermal treatment on a mixture consisting of heteropoly acid, copper salt, the rigid nitrogen-containing ligand and water after regulating and controlling the pH value, wherein the rigid nitrogen-containing ligand is 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole).
2. The method for preparing polyacid hybrid materials based on rigid nitrogen-containing ligand of claim 1, wherein the heteropoly acid is SiW12The copper salt is Cu (NO)3)2·3H2The preparation method specifically comprises the following steps:
adding Cu (NO)3)2·3H2O，SiW12Adding 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) and water into a polytetrafluoroethylene-lined high-pressure stainless steel reaction kettle, adjusting the pH to 3.5, sealing, placing the reaction kettle in an oven, reacting at 160 ℃ for 3 days, and purifying to obtain the copper-based copper alloy3)2·3H2O、SiW12The mol volume ratio of the 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) to the water is 0.5 mmol: 0.1 mmol: 0.1 mmol: 10 mL.
3. The method for preparing polyacid hybrid materials based on rigid nitrogen-containing ligand of claim 2, characterized in that HNO is used3The solution and NaOH solution were used to adjust the pH.
4. The method for preparing polyacid hybrid materials based on rigid nitrogen-containing ligand of claim 1, wherein the heteropoly acid is PMo12The copper salt is Cu (OAc)2The preparation method specifically comprises the following steps:
general formula (Cu), (OAc)2，PMo124' - (1, 4-phenyl)Adding bis (4H-1,2, 4-triazole) and water into a polytetrafluoroethylene-lined high-pressure stainless steel reaction kettle, adjusting pH to 4.5, sealing, placing the reaction kettle in an oven, reacting at 160 ℃ for 3 days, and purifying to obtain the product, wherein Cu (OAc)2、PMo12The mol volume ratio of the 4' - (1, 4-phenyl) bis (4H-1,2, 4-triazole) to the water is 1.2 mmol: 0.075 mmol: 0.2 mmol: 10 mL.
5. The method for preparing polyacid hybrid materials based on rigid nitrogen-containing ligands of claim 4, wherein pH is adjusted with HCl solution and NaOH solution.
6. A polyacid hybrid material based on a rigid nitrogen-containing ligand, characterized in that it is prepared by the preparation method of claim 3 and has the chemical formula C10Cu2N6O23Si0.5W6Na0.25Wherein the crystal system is a monoclinic system; space group is P21C; unit cell parameter of
Figure FDA0002313891160000011
Figure FDA0002313891160000012
α＝90°、β＝105.001(4)°、γ＝90°、Z＝4。
7. A polyacid hybrid material based on rigid nitrogen-containing ligands, characterized in that it is prepared by the preparation method of claim 5, and its chemical formula is C5H4Cu1.25N3O, wherein the crystal system is a tetragonal crystal system; space group I41(ii)/amd; unit cell parameter of
Figure FDA0002313891160000021
α＝90°、β＝90°、γ＝90°、Z＝16。
8. Use of the polyacid hybrid material based on rigid nitrogen-containing ligands of any one of claims 6 to 7 as a photodegradation catalyst for degrading rhodamine B.
CN201911269972.XA 2019-12-11 2019-12-11 Polyacid hybrid material based on rigid nitrogen-containing ligand, preparation method and application Pending CN110894300A (en)

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CN114790297A (en) * 2022-04-02 2022-07-26 东南大学 Crystal state reduction-oxidation cluster-based complex and preparation method and application thereof
CN114874449A (en) * 2022-04-28 2022-08-09 南阳理工学院 Preparation method and application of metal-organic framework compound containing single-atom catalytic site

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